Release of nanoparticle coatings additives from common surfaces via simulated dermal contact.

Both nanoparticles (NPs) and nano-enabled products have become widely available in consumer markets in the last decade. Surface coating including paints, stains, and sealants, have seen large increases in the inclusion of nanomaterials in their formulations to increase UV resistance, hydrophobicity, and scratch resistance. Currently, most literature studying the release of NPs and byproducts from coated surfaces has focused exclusively on lumber. In this study, well characterized CeO2 NPs were dispersed in either Milli-Q water, or a commercial paint primer and applied to several test surfaces including sanded plywood, drywall, low density polyethylene, acrylonitrile butadiene styrene, polycarbonate, textured polycarbonate with pebble finish, and glass. Coated surfaces were sampled using a method previously developed by U.S. Consumer Product Safety Commission staff to track the release of NPs via simulated dermal contact. Particular attention has been paid to the total amount, and morphology of material released. The total amount of cerium released from coated surfaces was found to be dependent on both the identity of the test surface, as well as the solution used for coating. Water-based application found 22-50 % of the applied cerium removed during testing, while primer-based application showed released rates ranging between 0.1 and 3 %. Finally, the SEM micrographs presented here suggest the release of microplastic particles during simulated dermal contact with plastic surfaces.

Exposure to emissions generated by 3-dimensional printing with polycarbonate: effects on peripheral vascular function, cardiac vascular morphology and expression of markers of oxidative stress in male rat cardiac tissue.

Three-dimensional (3D) printing with polycarbonate (PC) plastic occurs in manufacturing settings, homes, and schools. Emissions generated during printing with PC stock and bisphenol-A (BPA), an endocrine disrupter in PC, may induce adverse health effects. Inhalation of 3D printer emissions, and changes in endocrine function may lead to cardiovascular dysfunction. The goal of this study was to determine whether there were any changes in markers of peripheral or cardiovascular dysfunction in animals exposed to PC-emissions. Male Sprague Dawley rats were exposed to PC-emissions generated by 3D printing for 1, 4, 8, 15 or 30 d. Exposure induced a reduction in the expression of the antioxidant catalase (Cat) and endothelial nitric oxide synthase (eNos). Endothelin and hypoxia-induced factor 1α transcripts increased after 30 d. Alterations in transcription were associated with elevations in immunostaining for estrogen and androgen receptors, nitrotyrosine, and vascular endothelial growth factor in cardiac arteries of PC-emission exposed animals. There was also a reduction eNOS immunostaining in cardiac arteries from rats exposed to PC-emissions. Histological analyses of heart sections revealed that exposure to PC-emissions resulted in vasoconstriction of cardiac arteries and thickening of the vascular smooth muscle wall, suggesting there was a prolonged vasoconstriction. These findings are consistent with studies showing that inhalation 3D-printer emissions affect cardiovascular function. Although BPA levels in animals were relatively low, exposure-induced changes in immunostaining for estrogen and androgen receptors in cardiac arteries suggest that changes in the action of steroid hormones may have contributed to the alterations in morphology and markers of cardiac function.

Pulmonary evaluation of whole-body inhalation exposure of polycarbonate (PC) filament 3D printer emissions in rats.

During fused filament fabrication (FFF) 3D printing with polycarbonate (PC) filament, a release of ultrafine particles (UFPs) and volatile organic compounds (VOCs) occurs. This study aimed to determine PC filament printing emission-induced toxicity in rats via whole-body inhalation exposure. Male Sprague Dawley rats were exposed to a single concentration (0.529 mg/m3, 40 nm mean diameter) of the 3D PC filament emissions in a time-course via whole body inhalation for 1, 4, 8, 15, and 30 days (4 hr/day, 4 days/week), and sacrificed 24 hr after the last exposure. Following exposures, rats were assessed for pulmonary and systemic responses. To determine pulmonary injury, total protein and lactate dehydrogenase (LDH) activity, surfactant proteins A and D, total as well as lavage fluid differential cells in bronchoalveolar lavage fluid (BALF) were examined, as well as histopathological analysis of lung and nasal passages was performed. To determine systemic injury, hematological differentials, and blood biomarkers of muscle, metabolic, renal, and hepatic functions were also measured. Results showed that inhalation exposure induced no marked pulmonary or systemic toxicity in rats. In conclusion, inhalation exposure of rats to a low concentration of PC filament emissions produced no significant pulmonary or systemic toxicity.

Inhalation of polycarbonate emissions generated during 3D printing processes affects neuroendocrine function in male rats.

Three-dimensional (3D) printing of manufactured goods has increased in the last 10 years. The increased use of this technology has resulted in questions regarding the influence of inhaling emissions generated during printing. The goal of this study was to determine if inhalation of particulate and/or toxic chemicals generated during printing with polycarbonate (PC) plastic affected the neuroendocrine system. Male rats were exposed to 3D-printer emissions (592 µg particulate/m3 air) or filtered air for 4 h/day (d), 4 days/week and total exposures lengths were 1, 4, 8, 15 or 30 days. The effects of these exposures on hormone concentrations, and markers of function and/or injury in the olfactory bulb, hypothalamus and testes were measured after 1, 8 and 30 days exposure. Thirty days of exposure to 3D printer emissions resulted in reductions in thyroid stimulating hormone, follicle stimulating hormone and prolactin. These changes were accompanied by (1) elevation in markers of cell injury; (2) reductions in active mitochondria in the olfactory bulb, diminished gonadotropin releasing hormone cells and fibers as well as less tyrosine hydroxylase immunolabeled fibers in the arcuate nucleus; and (3) decrease in spermatogonium. Polycarbonate plastics may contain bisphenol A, and the effects of exposure to these 3D printer-generated emissions on neuroendocrine function are similar to those noted following exposure to bisphenol A.

Evaluation of Pulmonary Effects of 3-D Printer Emissions From Acrylonitrile Butadiene Styrene Using an Air-Liquid Interface Model of Primary Normal Human-Derived Bronchial Epithelial Cells.

This study investigated the inhalation toxicity of the emissions from 3-D printing with acrylonitrile butadiene styrene (ABS) filament using an air-liquid interface (ALI) in vitro model. Primary normal human-derived bronchial epithelial cells (NHBEs) were exposed to ABS filament emissions in an ALI for 4 hours. The mean and mode diameters of ABS emitted particles in the medium were 175 ± 24 and 153 ± 15 nm, respectively. The average particle deposition per surface area of the epithelium was 2.29 × 107 ± 1.47 × 107 particle/cm2, equivalent to an estimated average particle mass of 0.144 ± 0.042 µg/cm2. Results showed exposure of NHBEs to ABS emissions did not significantly affect epithelium integrity, ciliation, mucus production, nor induce cytotoxicity. At 24 hours after the exposure, significant increases in the pro-inflammatory markers IL-12p70, IL-13, IL-15, IFN-γ, TNF-α, IL-17A, VEGF, MCP-1, and MIP-1α were noted in the basolateral cell culture medium of ABS-exposed cells compared to non-exposed chamber control cells. Results obtained from this study correspond with those from our previous in vivo studies, indicating that the increase in inflammatory mediators occur without associated membrane damage. The combination of the exposure chamber and the ALI-based model is promising for assessing 3-D printer emission-induced toxicity.

Quantifying Mechanical Abrasion of MWCNT Nanocomposites Used in 3D Printing: Influence of CNT Content on Abrasion Products and Rate of Microplastic Production.

Manufactured nanomaterials (MNMs) are incorporated as "nanofillers" into consumer products to enhance properties of interest. Multiwalled carbon nanotubes (MWCNTs) are known for their unique properties and have many applications in polymers. However, the release of MWCNTs during the nanoenabled product life cycle is concerning. During the use phase, mechanical stresses can produce fragmented materials containing MNMs. The degree of MNM release, the resulting exposure to these materials, and the potential impacts of their release are active research topics. In this study, we describe methodological improvements to study the abrasion of plastics containing MNMs (nanocomposites) and report on characteristics of abrasion products produced and rates of microplastic production. The abrasion device developed for this work allows for the measurement of power inputs to determine scaled release rates. Abrasion rates for plastics used in 3D printing were found to be 0.27 g/m2/s for the PETG polymer and 0.3 g/m2/s for the 2% MWCNT-PETG nanocomposite. Embedded and protuberant MWCNTs appeared to impact the particle size, shape, hydrophobicity, and surface charge of the microplastics, while the inclusion of MWCNTs had a small effect on microplastic production. Measurements of power input to the abrasion process provided a basis for estimating microplastic production rates for these nanocomposites.

Impacts of ingested MWCNT-Embedded nanocomposites in Japanese medaka (Oryzias latipes).

Polymer nanocomposites combine the versatile, lightweight characteristics of polymers with the properties of nanomaterials. Polyethylene terephthalate glycol (PETG) is commonly used in polymer additive manufacturing due to its controllable transparency, high modulus, and mechanical properties. Multi-walled carbon nanotubes (MWCNTs) add tensile strength, electrical conductivity, and thermal stability. The increased use of nanocomposites has led to concern over potential human health risks. We assessed morphologic alterations to determine impacts of ingested abraded nanocomposites compared to its component materials, pristine MWCNTs (1000 mg/L) and PETG. Adult transparent Japanese medaka (Oryzias latipes) were administered materials via oral gavage in 7 doses over 16 days. In vivo observations revealed altered livers and gallbladders following exposure to pristine MWCNTs and nanocomposites. Subsequent histologic sections showed fish exposed to pristine MWCNTs had highly altered biliary structures, and exposure to nanocomposites resulted in hepatocellular alteration. Thyroid follicle proliferation was also observed in fish exposed to materials containing MWCNTs. Transmission electron microscopy of livers showed that hepatocytes of fish exposed to MWCNTs had widespread swelling of rough endoplasmic reticulum, pronounced lysosomal activity, and swelling of intrahepatic biliary passageways. Fish exposed to nanocomposites had areas of degenerated hepatocytes with interspersed cellular debris. Each analysis showed that fish exposed to pristine PETG were most similar to controls. These results suggest that MWCNTs are the source of toxicity in abraded nanocomposite materials but that nanocomposites may also have some unique effects. The similarities of many teleost and mammalian tissues are such that these findings may indicate human health risks.

Pulmonary and systemic toxicity in rats following inhalation exposure of 3-D printer emissions from acrylonitrile butadiene styrene (ABS) filament.

BACKGROUND: Fused filament fabrication 3-D printing with acrylonitrile butadiene styrene (ABS) filament emits ultrafine particulates (UFPs) and volatile organic compounds (VOCs). However, the toxicological implications of the emissions generated during 3-D printing have not been fully elucidated. AIM AND METHODS: The goal of this study was to investigate the in vivo toxicity of ABS-emissions from a commercial desktop 3-D printer. Male Sprague Dawley rats were exposed to a single concentration of ABS-emissions or air for 4 hours/day, 4 days/week for five exposure durations (1, 4, 8, 15, and 30 days). At 24 hours after the last exposure, rats were assessed for pulmonary injury, inflammation, and oxidative stress as well as systemic toxicity. RESULTS AND DISCUSSION: 3-D printing generated particulate with average particle mass concentration of 240 ± 90 µg/m³, with an average geometric mean particle mobility diameter of 85 nm (geometric standard deviation = 1.6). The number of macrophages increased significantly at day 15. In bronchoalveolar lavage, IFN-γ and IL-10 were significantly higher at days 1 and 4, with IL-10 levels reaching a peak at day 15 in ABS-exposed rats. Neither pulmonary oxidative stress responses nor histopathological changes of the lungs and nasal passages were found among the treatments. There was an increase in platelets and monocytes in the circulation at day 15. Several serum biomarkers of hepatic and kidney functions were significantly higher at day 1. CONCLUSIONS: At the current experimental conditions applied, it was concluded that the emissions from ABS filament caused minimal transient pulmonary and systemic toxicity.

Selection of an Optimal Abrasion Wheel Type for Nano-Coating Wear Studies under Wet or Dry Abrasion Conditions.

Nanocoatings have numerous potential applications in the indoor environment, such as flooring finishes with increased scratch- and wear-resistance. However, given concerns about the potential environmental and human health effects of nanomaterials, it is necessary to develop standardized methods to quantify nanomaterial release during use of these products. One key choice for mechanical wear studies is the abrasion wheel. Potential limitations of different wheels include the release of fragments from the wheel during abrasion, wearing of the wheel from the abrasion process, or not releasing a sufficient number of particles for accurate quantitative analysis. In this study, we evaluated five different wheels, including a typically used silicon oxide-based commercial wheel and four wheels fabricated at the National Institute of Standards and Technology (NIST), for their application in nanocoating abrasion studies. A rapid, nondestructive laser scanning confocal microscopy method was developed and used to identify released particles on the abraded surfaces. NIST fabricated a high performing wheel: a noncorrosive, stainless-steel abrasion wheel containing a deep cross-patch. This wheel worked well under both wet and dry conditions, did not corrode in aqueous media, did not release particles from itself, and yielded higher numbers of released particles. These results can be used to help develop a standardized protocol for surface release of particles from nanoenabled products using a commercial rotary Taber abraser.

Acrylonitrile butadiene styrene (ABS) and polycarbonate (PC) filaments three-dimensional (3-D) printer emissions-induced cell toxicity.

During extrusion of some polymers, fused filament fabrication (FFF) 3-D printers emit billions of particles per minute and numerous organic compounds. The scope of this study was to evaluate FFF 3-D printer emission-induced toxicity in human small airway epithelial cells (SAEC). Emissions were generated from a commercially available 3-D printer inside a chamber, while operating for 1.5 h with acrylonitrile butadiene styrene (ABS) or polycarbonate (PC) filaments, and collected in cell culture medium. Characterization of the culture medium revealed that repeat print runs with an identical filament yield various amounts of particles and organic compounds. Mean particle sizes in cell culture medium were 201 ±â€¯18 nm and 202 ±â€¯8 nm for PC and ABS, respectively. At 24 h post-exposure, both PC and ABS emissions induced a dose dependent significant cytotoxicity, oxidative stress, apoptosis, necrosis, and production of pro-inflammatory cytokines and chemokines in SAEC. Though the emissions may not completely represent all possible exposure scenarios, this study indicate that the FFF could induce toxicological effects. Further studies are needed to quantify the detected chemicals in the emissions and their corresponding toxicological effects.

Long-term wear effects on nanosilver release from commercially available food contact materials.

Potential consumer exposure to nanoparticles (NPs) from nanoenabled food contact materials (FCMs) has been a driving force for migration studies of NPs from FCMs. Although NP migration from fresh, unused FCMs was not previously observed, conditions that result in significant changes to the surface of FCMs have not been investigated for NP migration into food. Therefore, a quantitative assessment of nanoparticle release from commercially available nanosilver-enabled FCMs was performed using an abrasion protocol to simulate cleaning, cutting, scraping and other stressful use conditions. Laser scanning confocal microscopy (LSCM) analysis showed a general increase in root mean square (RMS) roughness after FCM abrasion, and particle count (for particle sizes from 80 nm to 960 nm) at the surface was 4 orders of magnitude higher for the abraded FCMs. Migration was evaluated using both water and 3% (v/v, volume fraction) acetic acid as food simulants. Low concentrations of total Ag were detected in water simulants with a small portion (<10 ng dm-2) in the form of silver nanoparticles (AgNPs). Median particle diameter ranged from 39 nm to 50 nm with particle number concentrations on the order of 106 particles dm- 2. Total Ag migration into 3% (v/v) acetic acid was significantly higher than in water; however, 3% (v/v) acetic acid was not suitable for evaluation of NP release due to dissolution of AgNPs to Ag+ under acidic solution chemistries.

Transformation and release of nanoparticle additives & byproducts from commercially available surface coatings on pressure treated lumber via dermal contact.

Production and marketing of "nano-enabled" products for consumer purchase has continued to expand. However, many questions remain about the potential release and transformation of these nanoparticle (NP) additives from products throughout their lifecycle. In this work, two surface coating products advertised as containing ZnO NPs as active ingredients, were applied to micronized copper azol (MCA) and aqueous copper azol (ACA) pressure treated lumber. Coated lumber was weathered outdoors for a period of six months and the surface was sampled using a method developed by the Consumer Product Safety Commission (CPSC) to track potential human exposure to ZnO NPs and byproducts through simulated dermal contact. Using this method, the total amount of zinc extracted during a single sampling event was <1 mg/m2 and no evidence of free ZnO NPs was found. Approximately 0.5% of applied zinc was removed via simulated dermal contact over 6-months, with increased weathering periods resulting in increased zinc release. XAFS analysis found that only 27% of the zinc in the as received coating could be described as crystalline ZnO and highlights the transformation of these mineral phases to organically bound zinc complexes during the six-month weathering period. Additionally, SEM images collected after sampling found no evidence of free NP ZnO release during simulated dermal contact. Both simulated dermal contact experiments, and separate leaching studies demonstrate the application of surface coating solutions to either MCA and ACA lumber will reduce the release of copper from the pressure treated lumber. This work provides clear evidence of the transformation of NP additives in consumer products during their use stage.

Toxicological assessment of dust from sanding micronized copper-treated lumber in vivo.

Micronized copper azole (MCA) is a lumber treatment improve longevity. In this study, the in vivo response to PM2.5 sanding dust generated from MCA-treated lumber was compared to that of untreated yellow pine (UYP) or soluble copper azole-treated (CA-C) lumber to determine if the MCA was more bioactive than CA-C. Mice were exposed to doses (28, 140, or 280 µg/mouse) of UYP, MCA, or CA-C sanding dust using oropharyngeal aspiration. Bronchoalveolar lavage fluid (BALF) lactate dehydrogenase activity was increased at 1 day post-exposure to 280 µg/mouse of MCA and CA-C compared to UYP. BALF polymorphonuclear cells were increased by MCA and CA-C. There were increases in BALF cytokines in MCA and CA-C-exposed groups at 1 day post-exposure. Lung histopathology indicated inflammation with infiltration of neutrophils and macrophages. Pulmonary responses were more severe in MCA and CA-C-exposed groups at 1 day post-exposure. MCA caused more severe inflammatory responses than CA-C at 1 day post-exposure. These findings suggest that the MCA and CA-C sanding dusts are more bioactive than the UYP sanding dust, and, moreover, the MCA sanding dust is more bioactive in comparison to the CA-C sanding dust. No chronic toxic effects were observed among all observed sanding dusts.

Release and transformation of ZnO nanoparticles used in outdoor surface coatings for UV protection.

A major area of growth for "nano-enabled" products has been the addition of nanoparticles (NPs) to surface coatings including paints, stains and sealants. Zinc oxide (ZnO) NPs, long used in sunscreens and sunblocks, have found growing use in surface coating formulations to increase their UV resistance, especially on outdoor products. In this work, ZnO NPs, marketed as an additive to paints and stains, were dispersed in Milli-Q water and a commercial deck stain. Resulting solutions were applied to either Micronized-Copper Azole (MCA) pressure treated lumber or a commercially available composite decking. A portion of coated surfaces were placed outdoors to undergo environmental weathering, while the remaining samples were stored indoors to function as experimental controls. Weathered and control treatments were subsequently sampled periodically for 6 months using a simulated dermal contact method developed by the Consumer Product Safety Commission (CPSC). The release of ZnO NPs, and their associated degradation products, was determined through sequential filtration, atomic spectroscopy, X-Ray Absorption Fine Structure Spectroscopy, and electron microscopy. Across all treatments, the percentage of applied zinc released through simulated dermal contact did not exceed 4%, although transformation and release of zinc was highly dependent on dispersion medium. For MCA samples weathered outdoors, water-based applications released significantly more zinc than stain-based, 180 ±â€¯28, and 65 ±â€¯9 mg/m2 respectively. Moreover, results indicate that the number of contact events drives material release.

Integrated Transcriptomics, Metabolomics, and Lipidomics Profiling in Rat Lung, Blood, and Serum for Assessment of Laser Printer-Emitted Nanoparticle Inhalation Exposure-Induced Disease Risks.

Laser printer-emitted nanoparticles (PEPs) generated from toners during printing represent one of the most common types of life cycle released particulate matter from nano-enabled products. Toxicological assessment of PEPs is therefore important for occupational and consumer health protection. Our group recently reported exposure to PEPs induces adverse cardiovascular responses including hypertension and arrythmia via monitoring left ventricular pressure and electrocardiogram in rats. This study employed genome-wide mRNA and miRNA profiling in rat lung and blood integrated with metabolomics and lipidomics profiling in rat serum to identify biomarkers for assessing PEPs-induced disease risks. Whole-body inhalation of PEPs perturbed transcriptional activities associated with cardiovascular dysfunction, metabolic syndrome, and neural disorders at every observed time point in both rat lung and blood during the 21 days of exposure. Furthermore, the systematic analysis revealed PEPs-induced transcriptomic changes linking to other disease risks in rats, including diabetes, congenital defects, auto-recessive disorders, physical deformation, and carcinogenesis. The results were also confirmed with global metabolomics profiling in rat serum. Among the validated metabolites and lipids, linoleic acid, arachidonic acid, docosahexanoic acid, and histidine showed significant variation in PEPs-exposed rat serum. Overall, the identified PEPs-induced dysregulated genes, molecular pathways and functions, and miRNA-mediated transcriptional activities provide important insights into the disease mechanisms. The discovered important mRNAs, miRNAs, lipids and metabolites may serve as candidate biomarkers for future occupational and medical surveillance studies. To the best of our knowledge, this is the first study systematically integrating in vivo, transcriptomics, metabolomics, and lipidomics to assess PEPs inhalation exposure-induced disease risks using a rat model.

Long-term wear effects on nanosilver release from commercially available food contact materials.

Potential consumer exposure to nanoparticles (NPs) from nanoenabled food contact materials (FCMs) has been a driving force for migration studies of NPs from FCMs. Although NP migration from fresh, unused FCMs was not previously observed, conditions that result in significant changes to the surface of FCMs have not been investigated for NP migration into food. Therefore, a quantitative assessment of nanoparticle release from commercially available nanosilver-enabled FCMs was performed using an abrasion protocol to simulate cleaning, cutting, scraping and other stressful use conditions. Laser scanning confocal microscopy (LSCM) analysis showed a general increase in root mean square (RMS) roughness after FCM abrasion, and particle count (for particle sizes from 80 nm to 960 nm) at the surface was 4 orders of magnitude higher for the abraded FCMs. Migration was evaluated using both water and 3% (v/v, volume fraction) acetic acid as food simulants. Low concentrations of total Ag were detected in water simulants with a small portion (<10 ng dm-2) in the form of silver nanoparticles (AgNPs). Median particle diameter ranged from 39 nm to 50 nm with particle number concentrations on the order of 106 particles dm- 2. Total Ag migration into 3% (v/v) acetic acid was significantly higher than in water; however, 3% (v/v) acetic acid was not suitable for evaluation of NP release due to dissolution of AgNPs to Ag+ under acidic solution chemistries.

Effects of consumer use practices on nanosilver release from commercially available food contact materials.

Migration evaluation involving nano-enabled food contact materials (FCMs) mostly focuses on potential nanoparticle release from new unused products. This may not represent consumer use practices encountered by the FCMs in their lifecycle. In order to determine if product use impacts the release of nanoparticles or other FCM components, it is necessary to perform migration evaluations under typical consumer use scenarios. A quantitative assessment of nanoparticle release from a commercially available nanosilver-enabled cutting board was performed under five conditions intended to simulate consumer use. Knife motion, washing and scratching scenarios were simulated by linear abrasion using knife blades, scrubbing pads and tungsten carbide burr attachments, respectively. Migration was evaluated using water and 3% acetic acid as food simulants. Low concentrations of silver (Ag) were detected in water simulants, a small portion (<4 ng dm-2) in the form of silver nanoparticles (AgNPs) with particle number concentrations on the order of 106 particles dm-2. Median particle diameter was 40 nm. Nanoparticle release into water was observed under all five consumer use scenarios studied, however there was no correlation with the different levels of stress simulated.

Physical chemical properties and cell toxicity of sanding copper-treated lumber.

To protect against decay and fungal invasion into the wood, the micronized copper, copper carbonate particles, has been applied in the wood treatment in recent years; however, there is little information on the health risk associated with sanding micronized copper-treated lumber. In this study, wood dust from the sanding of micronized copper azole-treated lumber (MCA) was compared to sanding dust from solubilized copper azole-treated wood (CA-C) and untreated yellow pine (UYP). The test found that sanding MCA released a much higher concentration of nanoparticles than sanding CA-C and UYP, and the particles between about 0.4-2 µm from sanding MCA had the highest percentage of copper. The percentage of copper in the airborne dust from sanding CA-C had a weak dependency on particle size and was lower than that from sanding MCA. Nanoparticles were seen in the MCA PM2.5 particles, while none were detected in the UYP or CA-C. Inductively coupled plasma mass spectrometry (ICP-MS) analysis found that the bulk lumber for MCA and CA-C had relatively equal copper content; however, the PM2.5 particles from sanding the MCA had a higher copper concentration when compared to the PM2.5 particles from sanding UYP or CA-C. The cellular toxicity assays show that exposure of RAW 264.7 macrophages (RAW) to MCA and CA-C wood dust suspensions did not induce cellular toxicity even at the concentration of 200 µg PM2.5 wood dust/mL. Since the copper from the treated wood dust can leach into the wood dust supernatant, the supernatants of MCA, CA-C and UYP wood dusts were subjected to the cellular toxicity assays. The data showed that at the higher concentrations of copper (≥5 µg/ml), both MCA and CA-C supernatants induced cellular toxicity. This study suggests that sanding MCA-treated lumber releases copper nanoparticles and both the MCA and CA-C-treated lumber can release copper, which are potentially related to the observed in vitro toxicity.

Dermal transfer and environmental release of CeO2 nanoparticles used as UV inhibitors on outdoor surfaces: Implications for human and environmental health.

A major area of growth for "nano-enabled" consumer products have been surface coatings, including paints stains and sealants. Ceria (CeO2) nanoparticles (NPs) are of interest as they have been used as additives in these these products to increase UV resistance. Currently, there is a lack of detailed information on the potential release, and speciation (i.e., ion vs. particle) of CeO2 NPs used in consumer-available surface coatings during intended use scenarios. In this study, both Micronized-Copper Azole pressure-treated lumber (MCA), and a commercially available composite decking were coated with CeO2 NPs dispersed in Milli-Q water or wood stain. Coated surfaces were divided into two groups. The first was placed outdoors to undergo environmental weathering, while the second was placed indoors to act as experimental controls. Both weathered surfaces and controls were sampled over a period of 6months via simulated dermal contact using methods developed by the Consumer Product Safety Commission (CPSC). The size and speciation of material released was determined through sequential filtration, total metals analysis, X-Ray Absorption Fine Structure Spectroscopy, and electron microscopy. The total ceria release from MCA coated surfaces was found to be dependent on dispersion matrix with aqueous applications releasing greater quantities of CeO2 than stain based applications, 66±12mg/m2 and 36±7mg/m2, respectively. Additionally, a substantial quantity of CeO2 was reduced to Ce(III), present as Ce(III)-organic complexes, over the 6-month experimental period in aqueous based applications.

Synergistic effects of engineered nanoparticles and organics released from laser printers using nano-enabled toners: potential health implications from exposures to the emitted organic aerosol.

Recent studies have shown that engineered nanoparticles (ENPs) are incorporated into toner powder used in printing equipment and released during their use. Thus, understanding the functional and structural composition and potential synergistic effects of this complex aerosol and released gaseous co-pollutants is critical in assessing their potential toxicological implications and risks. In this study, toner powder and PEPs were thoroughly examined for functional and molecular composition of the organic fraction and the concentration profile of 16 Environmental Protection Agency (EPA)-priority polycyclic aromatic hydrocarbons (PAH) using state of the art analytical methods. Results show significant differences in abundance of non-exchangeable organic hydrogen of toner powder and PEPs, with a stronger aromatic spectral signature in PEPs. Changes in structural composition of PEPs are indicative of radical additions and free-radical polymerization favored by catalytic reactions, resulting in formation of functionalized organic species. Particularly, accumulation of aromatic carbons with strong styrene-like molecular signatures on PEPs is associated with formation of semivolatile heavier aromatic species (i.e., PAHs). Further, the transformation of low molecular weight PAHs in the toner powder to high molecular weight PAHs in PEPs was documented and quantified. This may be a result of synergistic effects from catalytic metal/metal oxide ENPs incorporated into the toner and the presence/release of semi-volatile organic species (SVOCs). The presence of known carcinogenic PAHs on PEPs raises public health concerns and warrants further toxicological assessment.